Human exposure to sediment-borne contaminants is not directly related to chemical concentrations in the bulk sediment, but is instead controlled by the bioavailable concentration or bioavailability. Remediation practices, such as dredging, sand capping, sorbent amendment, and even monitored natural recovery (MNR) may all affect the bioavailability of sediment contaminants differently than the bulk sediment chemical concentration. In particular, bioavailability is a key to better assessing human exposure to hydrophobic organic contaminants (HOCs) such as DDT, PCBs, PAHs and dioxins through consumption of fish from contaminated areas. However, current methods for determining sediment HOC bioavailability suffer from method-specific limitations. Partial extraction techniques to estimate bioaccessibility are invariably influenced by types of extractants and extraction conditions selected. Passive samplers, including solid phase microextraction (SPME), must be used under equilibrium conditions that may take months to reach. In this project we exploit the wide availability of stable isotope labeled HOC compounds and GC-MS systems in two novel applications aiming to greatly improve the efficiency and accuracy of bioavailability measurement. The first approach uses the concept of isotope exchange (or dilution), similar to what has been done for trace elements, to derive the exchangeable concentration as an approximation of bioaccessible concentration. The fact that most HOCs are highly stable lends them the quality of being conservative and thus ideal for such an application. In the second approach, we incorporate stable isotope labeled HOCs with SPME by using the labeled HOCs as performance reference compounds so that SPME may be used under non-equilibrium conditions with short sampling time. The isotope exchange approach may be applied to ex situ assessment while the stable isotope- SPME method may be used for both ex situ and in situ measurements. We will carry out systematic studies to prove the underlying assumptions, develop and optimize the methods using spiked sediments, validate the methods through extensive bioaccumulation assays using a common fish prey (polychaete worm) and a deposit-feeding fish (California halibut), and then apply the methods for ex situ and in situ measurement of bioavailability of DDTs and PCBs at the Palos Verdes Shelf Superfund site off the coast of Los Angeles that has undergone pilot remediation trials and is scheduled for sand capping in 2012. At the end of this project, we expect to produce a range of rigorously tested methods that may be easily adopted for ex situ or in situ monitoring of sediment remediation sites to evaluate the effectiveness of remediation operations and predict changes in human exposure potential. PUBLIC HEALTH RELEVANCE: Human exposure to sediment-borne contaminants such as DDT, PCBs, PAHs and dioxins is not directly related to chemical concentrations in the bulk sediment, but is instead controlled by bioavailability. In this project we exploit the wide availability of stable isotope labeled HOC compounds and GC-MS systems in two novel applications aiming to greatly improve the efficiency and accuracy of bioavailability measurement. These methods may be easily adopted for ex situ or in situ monitoring of sediment remediation sites to evaluate the effectiveness of remediation operations and better predict changes in human exposure potential.